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AsFeP0 - A model concept for in situ investigation or arsenic and phosphate adsorption to predefined iron minerals and to characterize transformation processes of iron minerals

Shallow groundwater of the huge deltaic systems of Asia like the Red River Delta in Vietnam is often enriched in inorganic arsenic (As), threatening the health of millions of residents. The massive abstraction of groundwater in these areas locally causes an irreversible mixing of arsenic-free groundwater resources with arsenic-rich groundwater. Increased concentrations of competitive anions, especially phosphate (PO43-), decrease the immobilization capacity of the sediments. During transport, the mobility of dissolved As in local aquifers is strongly influenced by adsorption to sedimentary and ubiquitously occurring iron(oxyhydr)oxides. Additionally, arsenic-rich groundwater is often enriched in reduced iron (Fe2+) as well, which is capable to react with iron(oxyhydr)oxides, thereby inducing mineral transformations. Such transformations permanently affect the arsenic adsorption and immobilization capacity of the sediments.Within the scope of this research project, the underlying mechanisms related to As transport and the resulting threat to arsenic-free groundwater resources will be characterized in cooperation with the Swiss Federal Institute of Aquatic Science and Technology (Eawag). The research concept aims at assessing the complex interactions within the arsenic-iron-phosphate-system under field conditions at a study site next to the Red River. First, filtration experiments using local groundwater enriched in As and PO43- will be used to determine the As adsorption capacity of different and previously geochemically characterized iron(oxyhydr)oxides. In a second step, sample carrier containing As loaded iron(oxyhydr)oxides will be introduced into surface near aquifer parts of the study site (via existing groundwater monitoring wells). These samples will be exposed to local groundwater characterized by increased As, Fe2+ and PO43- concentrations for the following nine months. Using the in situ exposition of predefined iron(oxyhydr)oxides, it will be possible to distinguish potential mineral transformations and their influences on the As immobilization capacity of the respective iron(oxyhydr)oxides. By combining the results and outcomes of the field experiments, new and important conclusions regarding the mobility of As can be drawn. The data can be used to create a hydrochemical transport model describing reactive As transport within the investigation area. In addition, the results of the in situ exposition experiments will allow to draw conclusions in respective to the long term As immobilization capacity of different iron(oxyhydr)oxides, which is an essential information regarding in situ decontamination techniques.

Community-mediated mechanisms to stabilize pollination of agricultural production highly dependent on shrinking honey bee populations under global change

Almond in California represents an agroecosystem pollinated solely by a single species, the European honey bee, a species that is becoming increasingly difficult and expensive to manage due to substantial, unpredictable mortality. Therefore, sustainable and high output production require a more integrated approach that diversifies sources of pollination. For this purpose, detailed data of our understanding how diversity can stabilize pollination are required. The project will identify alternative wild pollinator species and collect high quality data contributing to our understanding of how diversity (pollen and insects) can bolster honey bee pollination during stable and unstable climatic conditions. The research will be carried out on almond orchards in Northern California known to be either pollinator species rich (up to 30 species) or depauperate (honey bees only). The replicated extremes in pollinator diversity represent a unique opportunity to study the effects of diversity on pollination in real agroecosystems combined with laboratory and glasshouse experiments. The overall goal is to provide basic research that is essential for our general understanding of how insect diversity can affect high-quality pollination under land use and climate change.

Biogenic formation of non-extractable residues from pesticides in soil

During microbial turnover of organic chemicals in soil, non-extractable residues (NER) are formed frequently. Studies on NER formation usually performed with radioisotope labelled tracer compounds are limited to localisation and quantitative analyses but their chemical composition is left unknown. Recently, we could show for 2,4-dichlorophenoxyacetic acid and ibuprofen that during microbial turnover in soil nearly all NER were derived from microbial biomass, since degrading bacteria use the pollutant carbon for their biomass synthesis. Their cell debris is subsequently stabilised within soil organic matter (SOM) forming biogenic NER (bioNER). It is still unknown whether bioNER are also formed during biodegradation of other, structurally different compound classes of organic contaminants. Therefore, agricultural soil will be incubated with labelled compounds of five classes of commonly used and emerging pesticides: organophosphate, phenylurea, triazinone, benzothiadiazine and aryloxyphenoxypropionic acid. The fate of the label will be monitored in both living and non-living SOM pools and the formation of bioNER will be quantified for each compound over extended periods of time. In addition, soil samples from long-term lysimeter studies with 14C-labelled pesticide residues (e.g. triazine, benzothiazole and phenoxypropionic acid group) will be also analysed for bioNER formation. The results will be summarised to identify the metabolic conditions of microorganisms needed for bioNER formation and to develop an extended concept of risk assessment including bioNER formation in soils.

Biogenic soil structures: feedbacks between bioactivity and spatial heterogeneity of water storage and fluxes from plot to hillslope scale

Soil structure determines a large part of the spatial heterogeneity in water storage and fluxes from the plot to the hillslope scale. In recent decades important progress in hydrological research has been achieved by including soil structure in hydrological models. One of the main problems herein remains the difficulty of measuring soil structure and quantifying its influence on hydrological processes. As soil structure is very often of biogenic origin (macropores), the main objective of this project is to use the influence of bioactivity and resulting soil structures to describe and support modelling of hydrological processes at different scales. Therefore, local scale bioactivity will be linked to local infiltration patterns under varying catchment conditions. At hillslope scale, the spatial distribution of bioactivity patterns will be linked to connectivity of subsurface structures to explain subsurface stormflow generation. Then we will apply species distribution modelling of key organisms in order to extrapolate the gained knowledge to the catchment scale. As on one hand, bioactivity influences the hydrological processes, but on the other hand the species distribution also depends on soil moisture contents, including the feedbacks between bioactivity and soil hydrology is pivotal for getting reliable predictions of catchment scale hydrological behavior under land use change and climate change.

Schwerpunktprogramm (SPP) 1488: Planetary Magnetism (PlanetMag), Evolution of geomagnetic dipole moment and South Atlantic Anomaly

The geomagnetic field shields our habitat against solar wind and radiation from space. Due to the geometry of the field, the shielding in general is weakest at high latitudes. It is also anomalously weak in a region around the south Atlantic known as South Atlantic Anomaly (SAA), and the global dipole moment has been decreasing by nearly 10 percent since direct measurements of field intensity became possible in 1832. Due to our limited understanding of the geodynamo processes in Earths core, it is impossible to reliably predict the future evolution of both dipole moment and SAA over the coming decades. However, lack of magnetic field shielding as would be a consequence of further weakening of dipole moment and SAA region field intensity would cause increasing problems for modern technology, in particular satellites, which are vulnerable to radiation damage. A better understanding of the underlying processes is required to estimate the future development of magnetic field characteristics. The study of the past evolution of such characteristics based on historical, archeo- and paleomagnetic data, on time-scales of centuries to millennia, is essential to detect any recurrences and periodicities and provide new insights in dynamo processes in comparison to or in combination with numerical dynamo simulations. We propose to develop two new global spherical harmonic geomagnetic field models, spanning 1 and 10 kyrs, respectively, and designed in particular to study how long the uninterrupted decay of the dipole moment has been going on prior to 1832, and if the SAA is a recurring structure of the field.We will combine for the first time all available historical and archeomagnetic data, both directions and intensities, in a spherical harmonic model spanning the past 1000 years. Existing modelling methods will be adapted accordingly, and existing data bases will be complemented with newly published data. We will further acquire some new archeomagnetic data from the Cape Verde islands from historical times to better constrain the early evolution of the present-day SAA. In order to study the long-term field evolution and possible recurrences of similar weak field structures in this region, we will produce new paleomagnetic records from available marine sediment cores off the coasts of West Africa, Brazil and Chile. This region is weakly constrained in previous millennial scale models. Apart from our main aim to gain better insights into the previous evolution of dipole moment and SAA, the models will be used to study relations between dipole and non-dipole field contributions, hemispheric symmetries and large-scale flux patterns at the core-mantle boundary. These observational findings will provide new insights into geodynamo processes when compared with numerical dynamo simulation results.Moreover, the models can be used to estimate past geomagnetic shielding above Earths surface against solar wind and for nuclide production from galactic cosmic rays.

Diffusion and advection with sorption of anions, cations and non-polar molecules in organo-clays at varying thermo-chemical conditions - validation by analytical methods and molecular simulation

The sorption of anions in geotechnical multibarrier systems of planned high level waste repositories (HLWR) and of non-ionic and organic pollutants in conventional waste disposals are in the center of recent research. In aquatic systems, persistent radionuclides such as 79Se, 99Tc, 129I exist in a form of anions. There is strongly increasing need to find materials with high sorption capacities for such pollutants. Specific requirements on barrier materials are long-term stability of adsorbent under various conditions such as T > 100 C, varying hydrostatic pressure, and the presence of competing ions. Organo-clays are capable to sorb high amounts of cations, anions and non-polar molecules simultaneously having selectivity for certain ions. This project is proposed to improve the understanding of sorption and desorption processes in organo-clays. Additionally, the modification of material properties under varying chemical and thermal conditions will be determined by performing diffusion and advection experiments. Changes by sorption and diffusion will be analyzed by determining surface charge and contact angles. Molecular simulations on models of organo-clays will be conducted in an accord with experiments with aim to understand and analyze experimental results. The computational part of the project will profit from the collaboration of German partner with the group in Vienna, which has a long standing experience in a modeling of clay minerals.

Ecosystem Engineering: Sediment entrainment and flocculation mediated by microbial produced extracellular polymeric substances (EPS)

Sediment erosion and transport is critical to the ecological and commercial health of aquatic habitats from watershed to sea. There is now a consensus that microorganisms inhabiting the system mediate the erosive response of natural sediments ('ecosystem engineers') along with physicochemical properties. The biological mechanism is through secretion of a microbial organic glue (EPS: extracellular polymeric substances) that enhances binding forces between sediment grains to impact sediment stability and post-entrainment flocculation. The proposed work will elucidate the functional capability of heterotrophic bacteria, cyanobacteria and eukaryotic microalgae for mediating freshwater sediments to influence sediment erosion and transport. The potential and relevance of natural biofilms to provide this important 'ecosystem service' will be investigated for different niches in a freshwater habitat. Thereby, variations of the EPS 'quality' and 'quantity' to influence cohesion within sediments and flocs will be related to shifts in biofilm composition, sediment characteristics (e.g. organic background) and varying abiotic conditions (e.g. light, hydrodynamic regime) in the water body. Thus, the proposed interdisciplinary work will contribute to a conceptual understanding of microbial sediment engineering that represents an important ecosystem function in freshwater habitats. The research has wide implications for the water framework directive and sediment management strategies.

Linking soil architecture formation with changing permafrost regime to carbon turnover in high latitude soils at multiple spatial scales

Most soils develop distinct soil architecture during pedogenesis and soil organic carbon (SOC) is sequestered within a hierarchical system of mineral-organic associations and aggregates. Permafrost soils store large amounts of carbon due to their permanently frozen subsoil and a lack of oxygen in the active layer, but they lack complex soil structure. With permafrost thaw more oxidative conditions and increasing soil temperature presumably enhance the build-up of more complex units of soil architecture and may counterbalance, at least partly, SOC mineralization. We aim to explore the development of mineral-organic associations and aggregates under different permafrost impact with respect to SOC stabilization. This information will be linked to environmental control factors relevant for SOC turnover at the pedon and stand scale to bridge processes occurring at the aggregate scale to larger spatial dimensions. We will combine in situ spectroscopic techniques with fractionation approaches and identify mechanisms relevant for SOC turnover at different scales by multivariate statistics and variogram analyses. From this we expect a deeper knowledge about soil architecture formation in the transition of permafrost soils to terrestrial soils and a scale-spanning mechanistic understanding of SOC cycling in permafrost regions.

Schwerpunktprogramm (SPP) 1685: Ecosystem nutrition: forest strategies for limited phosphorus resources; Ökosystemernährung: Forststrategien zum Umgang mit limitierten Phosphor-Ressourcen, Microbial P mobilization and immobilization in the rhizosphere and root-free soil (SPP: P Nutrition & recycling)

Soil microorganisms can mobilize and immobilize phosphorus (P), and therefore strongly affect the availability of P to plants. In this project we hypothesize that the ratio of labile P to microbial P increases during the transition from acquiring to recycling ecosystems. Microbial and plant P uptake will be studied with 33P that will be quantified in microbial and plant biomass as well as in lipids. To what extent microorganisms immobilize and mobilize P during decomposition of soil organic matter will be explored with a 14C/33P labeled monoester. Seasonal dynamics of actual and potential P mineralization (33P dilution and phosphatase activity), and microbial P immobilization will be studied with soils of the transition from acquiring to recycling ecosystems. The contribution of litter-derived P will be explored in a litter exclusion experiment in the field. Spatial patterns of microbial and plant P mineralization in the rhizosphere will be explored by analyses of areas of high acid and alkaline (=microbial-derived) phosphatase activity by soil zymography, and their relations with areas of high rhizodeposition (14C imaging). In conclusion, we will analyse mechanisms of actual and potential microbial P mineralization and immobilization, localization, and consequences for P uptake by plants.

Transport of EINP through soil affected by the dynamics of infiltration flux and particle properties

In this project we experimentally explore the transport of engineered inorganic nanoparticles (EINP) through soils. This is done for original EINPs and some pre-aged form. Transport of NPs in soil is expected to be different from that of reactive solutes, in that hydrodynamic drag, inertial and shear forces as well as the affinity to water-gas interfaces are expected to be more relevant. Hence, the mobility of EINPs in soil is highly sensitive to the morphology of the porous structure and the dynamics of water saturation.This project provides the pore network structure for natural soils using X-ray micro-tomography to allow for an up-scaling of pore-scale interactions explored by project partners to the scale of soil horizons. The pore structure is represented by a network model suitable for pore scale simulations including the dynamics of water-gas interfaces.Pore network simulations will be compared to column experiments for conservative tracers as well as for unaltered and pre-aged EINPs (obtained from INTERFACE). This includes steady state flow scenarios for saturated (ponding) and unsaturated conditions as well as for transient flow to explore the impact of moving water-gas interfaces. The final goal is to arrive at a consistent interpretation of experimental findings and numerical simulations to develop a module for modelling EINP transfer through soil as a function of particle properties, soil structural characteristics and external forcing in terms of flux boundary conditions.

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